CN114736424B - Asymmetric nano TiO 2 Particle-filled bionic super-smooth surface and preparation method and application thereof - Google Patents
Asymmetric nano TiO 2 Particle-filled bionic super-smooth surface and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of high molecular functional materials, and in particular relates to asymmetric nano TiO 2 Particle-filled bionic super-smooth surface, preparation method and application thereof, wherein functionalized cyclodextrin derivative obtained by esterifying cyclodextrin and maleic anhydride is subjected to copolymerization reaction with vinyl acetate and styrene to prepare amphiphilic cyclodextrin copolymer which is dissolved in TiCl-containing polymer 4 Preparing a film casting solution in carbon disulfide with the mass concentration of 0.1-1%, and then pouring the film casting solution on a glass sheet to obtain nano TiO 2 The static contact angle of the particle filled porous substrate can reach 143 degrees, and the static contact angle is improved by about 30 degrees. The prepared bionic super-smooth surface has excellent freezing resistance and biological bacteria adhesion resistance. Compared with a hydrophilic glass sheet with certain antibacterial adhesion, the antibacterial adhesion performance of the glass sheet is improved by 83.3 percent.
Description
Technical Field
The invention belongs to the field of high molecular functional materials, and in particular relates to asymmetric nano TiO 2 Particle-filled bionic super-smooth surface, and a preparation method and application thereof.
Background
Microparticles are of great interest for wide-ranging applications in the fields of optics, controlled release, biomedical, and the like. These applications depend on the chemical and physical properties of the particles, such as wettability, size and shape, etc., which are also important for their self-assembly. Among them, the specific asymmetric structure colloid particle system is very advantageous in creating complex structures by utilizing anisotropism, and meanwhile, the unique photon characteristics of the specific asymmetric structure colloid particle system also have wide application prospects in other fields.
Preparation of the bionic super-smooth surface is independent of substrate construction and grease injection, the construction of the substrate is crucial, and the substrate of the bionic super-smooth surface is a rough surface so as to achieve good oil injection rate and oil preservation effect. The porous rough surface has good application prospect in the fields of template materials, super-hydrophobic surfaces, separation membranes, sensing materials, biological materials, photoelectric materials and the like. In the SLIPS field, the porous material has higher oil injection rate and better oil locking effect, and the porous material brings attention to scientific researchers. Among the preparation methods, the water drop template method is a method which has relatively low cost, no pollution, simple operation and capability of manufacturing a porous rough film in a large area. Highly ordered hexagonal cell array membranes, known as honeycomb pattern membranes, have been prepared as early as 1911 using a water drop templating method. The technology was not originally developed by Francois and its colleagues until 1994, and related research reports were not initiated.
It is generally believed that the process of the water droplet templating method is such that when a polymer solution containing a low boiling point solvent is in a wet, closed environment, the solvent volatilizes causing a decrease in the temperature of the solution interface, and when water vapor contacts the interface, it condenses into water droplets upon cooling, which gradually grow under the synergistic effect of capillary action and Marangoni convection as the solvent volatilizes further, forming a uniform cellular porous structure. Therefore, parameters such as solvent, casting solution concentration, air humidity, polymer composition and structure can influence the microscopic morphology of the porous membrane. Because of the diversification of the influencing factors in the preparation process, the water drop template method can not realize industrialized application to date.
Disclosure of Invention
In order to overcome the problems, the invention provides a TiCl 4 Preparation of asymmetric nano TiO by auxiliary water drop template method 2 A preparation method and application of a particle-filled bionic super-smooth surface.
TiCl is used in a process based on a water droplet templating method 4 To improve the drop templating method. TiCl 4 Actively adsorb water vapor in the air, and then perform a series of reactions to obtain TiO 2 、H 2 O, HCl. H 2 O provides a porous structure for the material prepared by the water drop template method, HCl can directly volatilize and absorb heat to further condense water drops in the air on the surface, and TiO (titanium dioxide) 2 The particles can be used for filling hydrophobic materials to form an asymmetric system filling porous membrane, and simultaneously the nano TiO is generated 2 The interaction between the particles and the polymer plays a role similar to a cross-linking point, and has certain hydrophobic property and antibacterial property. Therefore, the prepared material has the advantages of hydrophobic property, heat resistance, antibacterial property and the like.
In order to achieve the purpose of the invention, the technical scheme adopted is as follows:
asymmetric nano TiO 2 The preparation method of the particle-filled bionic super-smooth surface comprises the following steps:
(1) Preparation of functionalized cyclodextrin derivatives
Mixing and grinding cyclodextrin and maleic anhydride into powder in a mortar, and carrying out esterification reaction under anhydrous condition to obtain a partially esterified CD derivative, namely the functionalized cyclodextrin derivative;
(2) Preparation of the copolymer
Adding a functionalized cyclodextrin derivative, azodiisobutyronitrile, vinyl acetate, styrene and tetrahydrofuran into a three-neck flask, condensing and refluxing under constant-temperature magnetic stirring, precipitating a copolymer by using a precipitant after the reaction is finished, filtering and drying to obtain the copolymer;
(3) Preparation of asymmetric nanoparticle-filled porous substrates
Weighing the copolymer prepared in the step (2) and dissolving the copolymer in TiCl-containing solution 4 Is prepared into casting film solution in carbon disulfide solvent, wherein TiCl 4 The mass concentration is 0.1-1%, the solution is poured on a glass sheet at room temperature under the ventilation condition, and the glass sheet is left to stand for full self-assembly, and then dried to obtain the nano TiO 2 Particle-filled porous substrates;
(4) Preparation of asymmetric nanoparticle-filled biomimetic ultra-smooth surface (SLIPS)
Nano TiO prepared in the step (3) is prepared 2 Immersing the particle-filled porous membrane into polydimethylsiloxane, filling the silicone oil into the hole fully, standing the sample vertically to make the surface grease be lost due to gravity, thus obtaining the nano TiO 2 Filling particles on the surface of the bionic SLIPS;
further, when the volume ratio of vinyl acetate to styrene is 1:1, the copolymer concentration is configured to be 10mg/mL, and the nano TiO is prepared 2 The particle filled porous membrane has good hydrophobic property, the static contact angle is 143 degrees, and the nano TiO 2 The particle filling bionic SLIPS surface has higher ice and freezing resistance and antibacterial adhesion resistance, the antibacterial adhesion resistance is improved by 83% compared with a glass sheet, and the antibacterial adhesion resistance is improved by 92% compared with a base material;
further, the functionalized cyclodextrin derivative in step (1) is prepared by the following method: mixing cyclodextrin and maleic anhydride in a mortar, grinding into powder, adding the powder into a conical flask, magnetically stirring at constant temperature until the powder is dissolved, continuously stirring until the solution is solidified into solid, repeatedly washing the product with acetone and ethanol for three times, and drying to obtain a partially esterified CD derivative, wherein the molar ratio of maleic anhydride to beta-cyclodextrin is 1:4-1:40;
further, in the step (1), the reaction temperature is 60-85 ℃, the reaction time is more than 6 hours, the solid block is required to be ground in the post-treatment process, the unreacted monomer is washed by acetone and ethanol, and the partial esterification CD derivative is obtained by suction filtration and drying at the temperature of 40-100 ℃;
further, in the step (2), 1g of the functionalized cyclodextrin derivative, the addition amount mass ratio of the vinyl acetate to the styrene is 1:18:9-36, the reaction conditions are that the reaction is carried out for more than 6 hours under the conditions of deoxidization, 60-80 ℃ and stirring, and the addition amount of the azodiisobutyronitrile is 1% of the mass of the monomer.
Further, the precipitant in the step (2) is methanol and water in a volume ratio of 1: 1;
further, the dropping amount of the casting solution on the glass in the step (3) is 50 to 200 mu L/cm 2 The reaction is carried out at room temperature (5-30 ℃), the air humidity is more than 50-80%, and the self-assembly time is more than 2 hours;
further, the soaking time in the step (4) is higher than 10min, and the vertical time is more than 24 h.
The bionic super-smooth surface obtained by the method is used as a hydrophobic material, an anti-icing material or an antibacterial adhesion material.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention uses acid anhydride to modify cyclodextrin into functional monomer, and introduces high active group while retaining the cavity structure of cyclodextrin, thereby facilitating chemical modification, and then through copolymerization reaction of styrene and vinyl acetate, the average substitution degree of functional CD monomer is 4, thus the copolymer with a certain branching degree can be prepared, and the copolymer has both styrene structural unit and vinyl acetate structural unit, so that the copolymer has better amphipathy. Is beneficial to the preparation of the porous structure by a water drop template method.
(2) The cyclodextrin has a stable cavity structure, and when a water-drop template method is used for preparing holes, a uniform multilayer hole structure can be prepared, so that the effects of higher oiling rate and oil locking are achieved. And little research work has been reported on the application of cyclodextrin materials to the SLIPS field, based on which the cyclodextrin copolymers are introduced to SLIPS. SLIPS with cyclodextrin structure as base material is prepared, and the oiling rate and oil locking effect of SLIPS are improved through cyclodextrin cavity structure.
(3) When the traditional water drop template method is used for preparing holes, the humidity, the temperature, the heat conduction capacity of a base material and the like are strictly controlled, and the hydrophobic property difference of the same batch of products is probably large, so that the industrial application is not realized so far as can be seen from the error bars of fig. 12 and 13, and TiCl is used in the method 4 At the same time, since the hydrophobic properties of the product are not only related to pores, tiO 2 The particles also have some hydrophobic ability and provide some coarse coarseness, so that the hydrophobic properties of the substrate are increased, and the preparation conditions can be carried out over a wide range of humidity and temperature. TiCl 4 Can adsorb water vapor in air to obtain coarse porous structure substrate, and the self-assembled TiO 2 The particles, like the diameter packing, do not have a small amount of particles that can react with hydroxyl groups on the cyclodextrin or through hydrogen bonding to adhere better to the porous substrate surface.
(4) The prepared super-smooth surface contains TiO 2 The particles can obviously improve the heat resistance of the material, and can improve the antibacterial adhesion performance of the material, and the lubricating grease layer on the ultra-smooth surface can continuously lead the inner antibacterial material TiO 2 The particles are slowly released, so that a long-term and efficient antibacterial adhesive material is achieved.
Drawings
FIG. 1 is an infrared spectrum of a cyclodextrin monomer and a functionalized cyclodextrin monomer of step (1) of example 1;
FIG. 2 is an infrared spectrum of cyclodextrin polymer 1 in step (2) of example 1;
FIG. 3 is a graph showing the ultraviolet absorption spectra of functionalized cyclodextrin and cyclodextrin polymer 1 of example 1;
FIG. 4 shows nano TiO in step (3) of example 1 2 Static contact angle pattern of particle-filled porous substrate;
FIG. 5 shows nano TiO in step (3) of example 1 2 Scanning electron microscope images of particle-filled porous films (a: 0.1%, b:0.3%, c:0.5%, d: 1%);
FIG. 6 is a TGA profile of SLIPS film in step (4) of example 1;
FIG. 7 is a DTG profile of SLIPS film in step (4) of example 1;
FIG. 8 shows nano TiO in step (4) of example 1 2 Static contact angle pattern of SLIPS films prepared with particle-filled porous substrates;
FIG. 9 is a 0.5wt% TiCl in step (4) of example 1 4 Sliding diagram of water droplets when the lower prepared SLIPS film is tilted 5 °;
FIG. 10 shows nano TiO in step (4) of example 2 2 Static contact angle pattern of SLIPS films prepared with particle-filled porous substrates;
FIG. 11 shows nano TiO in step (4) of example 3 2 Static contact angle pattern of SLIPS films prepared with particle-filled porous substrates;
FIG. 12 is a diagram showing nano TiO in step (3) of comparative example 1 2 Static contact angle pattern of particle-filled porous substrate;
FIG. 13 is a graph of comparative example 2 without nano TiO in step (3) 2 Static contact angle pattern of porous substrate of particles;
FIG. 14 is an anti-icing freeze plot of the hydrophobic film substrates of step (3) (4) and SLIPS samples of example 1 and comparative example 2;
FIG. 15 is an antibacterial adhesion chart of the hydrophobic film substrates of step (3) (4) and SLIPS samples in example 1 and comparative example 2;
FIG. 16 is an asymmetric nano TiO according to the present invention 2 Schematic preparation flow of particle-filled bionic super-slip surface.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in various other embodiments according to the present invention, or simply change or modify the design structure and thought of the present invention, which fall within the protection scope of the present invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention is further described in detail below in connection with the examples:
example 1:
(1) Preparing a functionalized cyclodextrin derivative;
500mg of cyclodextrin and 880mg of maleic anhydride are mixed and ground into powder in a mortar, then the powder is added into a 100mL conical flask, the mixture is stirred magnetically at the constant temperature of 80 ℃ until the powder is dissolved, then the mixture is stirred continuously until the solution is solidified into solid, the solid is soaked in acetone after 8 hours of reaction, the solid is required to be ground when the solid is in large size, the solid is washed with absolute ethyl alcohol, and the product is repeatedly washed with acetone and ethyl alcohol for three times respectively, and then the partially esterified CD derivative is obtained after drying.
FIG. 1 is an infrared spectrum of a beta-cyclodextrin monomer and a functionalized cyclodextrin derivative monomer, from which it can be seen that both curves have a cyclodextrin structure of 580cm -1 Ring vibration at site and 945cm -1 The skeleton containing alpha-1, 4 glycosidic bond vibrates at 1050cm -1 The absorption peak of (C) is the vibration absorption peak of-C-O-on the pyran ring. At 3445cm -1 The stretching vibration peaks of the hydroxyl groups appear nearby, which indicates that the two curves represent substances containing beta-cyclodextrin structures, while in curve 2, at 1722cm -1 The position with infrared characteristic vibration absorption peak is caused by symmetrical stretching vibration of unsaturated carboxylic acid, which indicates that the esterification reaction of maleic anhydride and cyclodextrin is carried out, namely, the successful preparation of the functionalized cyclodextrin monomer is shown;
(2) Preparing cyclodextrin copolymer;
1g of the functionalized cyclodextrin derivative, 1% azobisisobutyronitrile, 20mL of vinyl acetate, 20mL of styrene and 20mL of tetrahydrofuran were added to a 100mL three-necked flask, and nitrogen was purged to remove oxygen. The constant temperature magnetic stirring is started in advance, the temperature is set to be 70 ℃, after the temperature is stable, the deoxidized sealed three-neck flask is placed in equipment, and the condensation reflux reaction is carried out for 6 hours under the stirring of 400 revolutions per minute. After the reaction was completed, the semitransparent viscous liquid was dropped into anhydrous methanol with a dropper: distilled water volume ratio 1: and (3) precipitating, separating and drying the mixed solution of the cyclodextrin polymer 1 to finally obtain the cyclodextrin polymer 1.
FIG. 2 is an infrared spectrum of cyclodextrin polymer 1, from which at 3460cm -1 An infrared absorption stretching vibration peak corresponding to the hydroxyl is between 2900 and 3100cm -1 Within the range ofThe obvious infrared absorption peak corresponds to the telescopic vibration absorption peak of the benzene ring group and is at 757cm -1 And 697cm -1 The position corresponds to the characteristic absorption peak of the monosubstituted phenyl, and at the same time at 1722cm -1 There was an infrared absorption peak corresponding to the infrared absorption peak of the unsaturated carboxylic acid in the functionalized cyclodextrin monomer structure, which demonstrates the successful preparation of cyclodextrin copolymer 1.
FIG. 3 is a graph of UV absorption spectra of functionalized cyclodextrin versus cyclodextrin polymer 1, with simple cyclodextrin having no UV absorption over the test range. The cyclodextrin derivative has an unsaturated carboxylic acid structure, so curve a has an absorption peak of-c=o functionality at 207 nm; whereas curve b has an absorption peak for the-c=o function, and at 247nm there is also an absorption peak for the benzene ring on the corresponding styrene building block. This is consistent with infrared testing results, further demonstrating successful preparation of the partially esterified CD derivative and cyclodextrin copolymer. Combining with infrared analysis we can conclude that we have successfully prepared cyclodextrin copolymer 1.
(3) Preparing an asymmetric nanoparticle-filled porous substrate;
TiCl is added to the mixture 4 Dissolving in carbon disulfide to prepare 0.1%, 0.3%, 0.5% and 1% solution, using the solution as a solvent of a water drop template method, preparing 10mg/mL solution by using cyclodextrin copolymer 1 as a solute, performing ultrasonic treatment for 10min, pouring the solution onto a glass sheet under the condition of room temperature and air humidity of 60%, standing for 2h to fully self-assemble the solution, and then drying to obtain the nano TiO 2 The particles fill the porous membrane. The reaction formula is as follows:
TiCl 4 ·5H 2 O→TiOHCl 3 ·4H 2 O+HCl↑→Ti(OH) 2 Cl 2 ·3H 2 O+HCl↑ (1)
Ti(OH) 2 Cl 2 ·3H 2 O→Ti(OH) 3 Cl·2H 2 O+HCl↑→Ti(OH) 4 ·H 2 O+HCl↑ (2)
Ti(OH) 4 ·H 2 O→TiO 2 +3H 2 O (3)
FIG. 4 is a diagram of nano TiO 2 Static contact angle pattern of particle-filled porous substratesAnd (3) a sheet. As can be seen, with no TiCl added 4 The static contact angle of the porous film is only about 110 DEG, and TiCl is added 4 Will increase the static contact angle of the sample obviously when TiCl 4 When the content is higher than or equal to 0.5wt%, the static contact angle of the porous substrate sample reaches the highest, at this time, the static contact angle reaches about 143 degrees, and the hydrophobic property of the prepared substrate is more stable as can be seen from the error bar size of the graph.
FIG. 5 is a diagram of nano TiO 2 Scanning electron microscope pictures of particle-filled porous films (a: 0.1wt% TiCl 4 And b:0.3wt% TiCl 4 And c:0.5wt% TiCl 4 And d:1% by weight of TiCl 4 ). The self-assembly process is carried out by TiCl 4 Water vapor in the air can be adsorbed, so that the water drop template method hole making is realized. When TiCl 4 When the content is too low, a small amount of water is adsorbed, a small amount of small holes can be formed on the surface, and then the nano TiO is used 2 Particle filling, so that only a small amount of nano-spheres are arranged on the surface, the roughness is low, the hydrophobic property is poor, and the graph corresponds to FIG. 5a; with TiCl 4 The content is increased, the adsorbed water drops are increased, so that the water drops form a uniform hole structure on the surface, the oiling rate is continuously increased, the hydrophobic performance is increased, and the oiling rate is also increased (figure 5 b); when TiCl 4 The surface of FIG. 5c is formed when the content is gradually increased, wherein more micro-pores are present on the surface and TiO is also present in part of the pores 2 Micro-nano particles, and more micro-TiO exists on the surface of the film 2 The particles have a large surface roughness and thus a good hydrophobic property. When TiCl 4 When the content is increased to 1%, almost all the surface is coated with TiO 2 The packing, as in fig. 5d, itself has better hydrophobic properties but some small cracks appear.
(4) Preparation of SLIPS film
Nano TiO 2 The particle filled cellular porous membrane is immersed in polydimethylsiloxane for one day respectively, after silicone oil is fully injected, the sample is vertically stood for 24 hours, as the silicone oil enters the hole by siphoning, the silicone oil cannot flow out, superfluous lubricating grease on the surface is lost due to the action of gravity, and superfluous lubricating grease adsorbed on the surface is removed by using oil absorbing paper after standing, so that the bionic SLIPS surface is obtained。
FIGS. 6 and 7 are TGA and DTG graphs of SLIPS film, from which it can be seen that TiCl follows 4 The addition amount is increased, and the prepared nano TiO 2 The content of particles will also increase and the heat stability of the prepared SLIPS film will also increase. Unfilled TiO 2 The maximum decomposition temperature of the grease in the SLIPS film of (C) is 475 ℃, and the filler TiO is filled 2 The maximum decomposition temperature of the lubricating grease in the SLIPS film is about 600 ℃, and the heat resistance is obviously improved. At the same time it is easy to see TiO 2 The increased content of inorganic particles also improves the thermal stability of the cellular porous membrane, so that the thermal stability of the SLIPS membrane is obviously improved.
FIG. 8 shows the static contact angle of SLIPS films. As can be seen, when the SLIPS is prepared, the water drop directly contacts the surface of the silicone grease, and the contact angle of the ultra-smooth surface is about 120 DEG and is matched with TiCl 4 The addition amount of (2) has no obvious relation.
FIG. 9 shows TiCl at 0.5% by mass 4 From the sliding pictures of SLIPS films prepared below, it can be seen from the pictures that the prepared water drops have super-excellent sliding performance in the SLIPS films, meet the requirements of bionic super-sliding surface performance, and have TiCl at other mass ratios 4 The prepared ultra-slip surface has similar slip effect.
Example 2
(1) The esterification reaction was carried out to prepare a functionalized cyclodextrin derivative in the same manner as in example 1;
(2) Preparing cyclodextrin copolymer;
1g of the functionalized cyclodextrin derivative, 1% azobisisobutyronitrile, 20mL of vinyl acetate, 10mL of styrene and 20mL of tetrahydrofuran were added to a 100mL three-necked flask, and nitrogen was purged to remove oxygen. The constant temperature magnetic stirring is started in advance, the temperature is set to be 70 ℃, after the temperature is stable, the deoxidized sealed three-neck flask is placed in equipment, and the condensation reflux reaction is carried out for 6 hours under the stirring of 400 revolutions per minute. After the reaction was completed, the semitransparent viscous liquid was dropped into anhydrous methanol with a dropper: distilled water volume ratio 1: and (3) precipitating, separating and drying the mixed solution of the cyclodextrin polymer 1 to finally obtain the cyclodextrin polymer 2.
(3) Asymmetric nanoparticle filled porous substrates were prepared as in example 1;
(4) The preparation of SLIPS film was carried out in the same manner as in example 1.
FIG. 10 is a bar graph of SLIPS contact angle for copolymer 2 as a substrate, which is about 120℃because the water droplet directly contacts the surface of the silicone grease.
Example 3
(1) The esterification reaction was carried out to prepare a functionalized cyclodextrin derivative in the same manner as in example 1;
(2) Preparing cyclodextrin copolymer;
1g of the functionalized cyclodextrin derivative, 1% azobisisobutyronitrile, 20mL of vinyl acetate, 40mL of styrene and 20mL of tetrahydrofuran were added to a 100mL three-necked flask, and nitrogen was purged to remove oxygen. The constant temperature magnetic stirring is started in advance, the temperature is set to be 70 ℃, after the temperature is stable, the deoxidized sealed three-neck flask is placed in equipment, and the condensation reflux reaction is carried out for 6 hours under the stirring of 400 revolutions per minute. After the reaction was completed, the semitransparent viscous liquid was dropped into anhydrous methanol with a dropper: distilled water volume ratio 1: and (3) precipitating, separating and drying the mixed solution of the cyclodextrin polymer 3.
(3) Asymmetric nanoparticle filled porous substrates were prepared as in example 1;
(4) The preparation of SLIPS film was carried out in the same manner as in example 1.
FIG. 11 is a bar graph showing the contact angle of SLIPS prepared from copolymer 3 as a substrate, wherein the contact angle is about 120℃because the water droplet directly contacts the surface of the silicone grease when the SLIPS is prepared. Under this condition, the SLIPS film can be successfully prepared, and as can be seen from fig. 8, 10 and 11, the static contact angle of the prepared ultra-smooth surface is close due to the filling of the grease, but the better the hydrophobic property of the substrate is, the larger the surface roughness is, and the better the effect of injecting the silicone grease is.
Comparative example 1
(1) The esterification reaction was carried out to prepare a functionalized cyclodextrin derivative in the same manner as in example 1;
(2) Preparing cyclodextrin copolymer;
1g of the functionalized cyclodextrin derivative, 1% azobisisobutyronitrile, 20mL of vinyl acetate and 20mL of tetrahydrofuran were added to a 100mL three-necked flask, and nitrogen was purged to remove oxygen. The constant temperature magnetic stirring is started in advance, the temperature is set to be 70 ℃, after the temperature is stable, the deoxidized sealed three-neck flask is placed in equipment, and the condensation reflux reaction is carried out for 6 hours under the stirring of 400 revolutions per minute. After the reaction was completed, the semitransparent viscous liquid was dropped into anhydrous methanol with a dropper: distilled water volume ratio 1: and (3) precipitating, separating and drying the mixed solution of the polymer 1 to finally obtain the cyclodextrin polymer 4.
(3) Preparation of porous film
TiCl is added to the mixture 4 Dissolving in carbon disulfide to prepare a solution with the mass concentration of 0.5%, using the solution as a solvent of a water drop template method, using cyclodextrin copolymer 4 as a solute, preparing 10mg/mL, 20mg/mL, 30mg/mL, 40mg/mL and 50mg/mL solutions, carrying out ultrasound for 10min, pouring the solution onto a glass sheet under the condition of room temperature and air humidity of 60%, standing for 2h to fully self-assemble, and then drying to obtain the nano TiO 2 The particles fill the porous membrane.
Fig. 12 is a photograph showing the static contact angle of the porous film prepared by the method, and it can be found that the copolymer prepared under the condition does not contain a hydrophobic styrene structural unit, and meanwhile, the copolymer is prepared to have poor amphipathy because part of vinyl acetate is hydrolyzed to become alcohol and acid in the polymerization process and cyclodextrin has more hydrophilic hydroxyl groups, the film prepared by the water droplet template method is a hydrophilic film, and the surface of the film has no obvious pore structure.
(4) SLIPS film was prepared in the same manner as in example 1;
since the prepared substrate is a hydrophilic substrate and the surface of the substrate has no porous structure, oil is difficult to enter the inside of the substrate in the SLIPS preparation process, and the silicone oil is almost completely lost in the vertical suspension process, so that SLIPS preparation fails. In comparison with example 1, the absence of styrene addition in comparative example 1 resulted in a smooth and nonporous surface of the prepared substrate, and the substrate exhibited hydrophilicity, which resulted in failure of silicone oil to enter during the preparation of the SLIPS film, and the grease actually remaining on the surface during the post-treatment was also removed by the treatment, so that the SLIPS film could not be prepared.
Comparative example 2
(1) The esterification reaction was carried out to prepare a functionalized cyclodextrin derivative in the same manner as in example 1;
(2) The preparation method of the cyclodextrin copolymer is the same as that of example 1, example 2 and example 3 respectively;
(3) Preparing a porous membrane;
using CS only 2 The method is characterized in that cyclodextrin copolymer 1, copolymer 2 and copolymer 3 are respectively used as solutes, 10mg/mL of solution is prepared, after ultrasonic treatment is carried out for 10min, under the condition of room temperature, the air humidity is 60%, the solution is poured onto a glass sheet under the ventilation condition, standing is carried out for 2h to fully self-assemble the glass sheet, then the glass sheet is dried to form a film, the surface of the film is hydrophilic, and the water drop template method under the condition proves that a porous hydrophobic film cannot be prepared.
Experiments show that the conditions are changed into that the copolymer 1, the copolymer 2 and the copolymer 3 are respectively dissolved in a carbon disulfide solvent, and the solution with the concentration of 10mg/mL, 20mg/mL, 30mg/mL, 40mg/mL and 50mg/mL is prepared and is subjected to ultrasonic treatment for 10min. Adding half of water into constant temperature magnetic stirring, heating to 40 ℃, placing foam wrapped by tinfoil paper on the water surface, increasing the heat conducting property, placing 2 x 2cm glass sheets on the foam, sealing by using a cover until the humidity reaches 100%, measuring 100-300 mu L of solution by using a pipette, uniformly pouring on the glass sheets, self-assembling for more than 2 hours, and then drying in a baking oven at 70 ℃ to obtain the honeycomb porous membrane.
FIG. 13 is a photograph showing the static contact angle of a porous film (copolymer 1 for a, copolymer 2 for b, and copolymer 3 for c,) prepared at 40℃and 100% humidity. A porous film having hydrophobic properties can be produced only when the humidity is as high as 100%, and the film has no TiO 2 Filling, its highest contact angle is only 138 °, while in FIG. 8 it can be seen that TiCl when 4 When the concentration is 0.5%, the contact angle of the particle filling prepared is up to 143 degrees, and the hydrophobic property of the film prepared by the single water drop template method can be lower than that of TiO 2 The heat resistance of the filled film is also worse.
In contrast to the examples, tiCl was not used in the drop templating process 4 The compound is used as a carrier of a compound,the results show that the water drop template method can not prepare the porous hydrophobic membrane under the condition of low humidity (60%), the hydrophobic membrane with porous surface can be prepared only when the water temperature reaches 40 ℃ and the humidity reaches 100% in the closed container, and the hydrophobic property is still lower than TiCl 4 TiO prepared by improved water drop template method 2 And filling the film. Thus TiCl is used 4 The stringent requirements of temperature and wetland in the water drop templating method can be reduced, and the hydrophobic properties of the membrane are improved.
(4) Preparation of SLIPS film
Respectively immersing the honeycomb porous membrane into polydimethylsiloxane for one day, fully injecting the silicone oil, vertically standing the sample for 24 hours, enabling the silicone oil to enter the hole by means of siphonage, preventing outflow, enabling superfluous lubricating grease on the surface to run off under the action of gravity, and removing superfluous lubricating grease adsorbed on the surface by using oil absorption paper after standing to obtain the bionic SLIPS surface.
FIG. 14 is an anti-icing and anti-freezing graph of the hydrophobic film substrates and SLIPS samples of example 1 and comparative example 2, the materials were frozen in tap water at-20℃for one day, and the contact angle was measured for the changes before and after. From the figure, it can be seen that the hydrophobic property of the hydrophobic film is obviously reduced, the static contact angles of the samples 1 and 2 are respectively reduced by 18 degrees and 17 degrees, and the surface of the sample is obviously damaged to a certain degree. Whereas the hydrophobic properties of SLIPS are essentially unchanged, since the membrane surface has methyl silicone oil infused, making ice more difficult to adhere to its surface. When water freezes, crystal nucleus is generated firstly, and is difficult to adhere to the surface of the lubricating grease layer, and even if a small amount of crystal nucleus is adhered to the surface, the crystal nucleus is protected by the liquid film layer, and even if the crystal nucleus is barely entered into the lubricating grease layer, the crystal nucleus is easy to fall off due to the fact that the surface has lower contact angle hysteresis, and the liquid lubricating grease can slowly flow to have self-repairing capability to a certain extent, so that the anti-icing and anti-freezing performance of the SLIPS film is excellent.
FIG. 15 is an antibacterial sticking chart of the hydrophobic porous membrane substrates and SLIPS membranes of example 1 and comparative example 2, from which it is evident that sample No. 2 has significantly more adhering colonies, even more than sample No. 1, i.e., a pure glass sheet. This is because the honeycomb porous film has a large roughness, and its specific surface area is remarkably increased, which is more favorable for bacterial attachment. We usePure glass sheet is control group, sample No. 3 is filled TiO 2 Hydrophobic film due to TiO 2 Has a certain level of bacteriostasis, so that the surface adhesion colony is reduced, but still more than that of a pure glass sheet. Compared with SLIPS film, the specific surface area of adhesion of coliform bacteria is obviously reduced because the SLIPS film is filled with the lubricating grease, and meanwhile, the lubricating grease has similar liquid characteristics and is more unfavorable for bacterial adhesion, so that only a small amount of bacteria adhere on the SLIPS film. And is filled with TiO 2 The antibacterial adhesion capacity of SLIPS of (C) is significantly higher due to the nano TiO in the substrate 2 Has certain antibacterial capability, and the TiO has the following characteristics 2 The antibacterial agent is slowly released from the holes, so that the SLIPS film has high antibacterial adhesion performance, the antibacterial adhesion performance is increased by 83% compared with a pure glass sheet, and the antibacterial adhesion performance is increased by 92% compared with a base material.
In comparison with example 1, comparative example 1 has no TiCl 4 The addition of (C) results in a failure to produce a rough surface at a lower humidity of 60%, even if the copolymer precipitates in powder form, which can prove TiCl 4 The addition of (3) can reduce the requirements of humidity and temperature in the water drop template method. And the prepared nano TiO 2 The filling SLIPS film has excellent heat resistance, ice and frost resistance and high-efficiency antibacterial adhesion resistance.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme and the concept of the present invention, and should be covered by the scope of the present invention.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme and the concept of the present invention, and should be covered by the scope of the present invention.
Claims (8)
1. Asymmetric nano TiO 2 The particle filling bionic super-smooth surface is characterized in that: the preparation method comprises the following steps:
(1) Preparation of functionalized cyclodextrin derivatives
Mixing and grinding cyclodextrin and maleic anhydride into powder in a mortar, and carrying out esterification reaction under anhydrous condition to obtain a functionalized cyclodextrin derivative;
(2) Preparation of the copolymer
Adding a functionalized cyclodextrin derivative, azodiisobutyronitrile, vinyl acetate, styrene and tetrahydrofuran into a reaction container, condensing and refluxing under constant-temperature magnetic stirring, precipitating a copolymer by using a precipitant after the reaction is finished, filtering and drying to obtain the copolymer;
(3) Preparation of asymmetric nanoparticle-filled porous substrates
Weighing the copolymer prepared in the step (2) and dissolving the copolymer in TiCl-containing solution 4 Is prepared into casting film solution in carbon disulfide solvent, wherein TiCl 4 The mass concentration is 0.1-1%, casting film liquid is poured on a glass sheet at room temperature under the ventilation condition, and the glass sheet is kept stand to fully self-assemble, and then dried, so that the nano TiO is obtained 2 Particle-filled porous substrates;
(4) Preparation of bionic super-smooth surface filled with asymmetric nano particles
Nano TiO prepared in the step (3) is prepared 2 Immersing the particle-filled porous substrate in polydimethylsiloxane, standing the sample vertically after the silicone oil is fully injected, so that superfluous lubricating grease on the surface is lost due to the action of gravity, and obtaining the asymmetric nanoparticle-filled bionic super-smooth surface;
in the step (2), the addition amount mass ratio of the functionalized cyclodextrin derivative of 1: 1g to the addition amount mass ratio of the vinyl acetate to the styrene is 1:18:9-36 respectively.
2. An asymmetric nano TiO according to claim 1 2 The preparation method of the particle filling bionic super-smooth surface is characterized by comprising the following steps of: the method comprises the following steps:
(1) Preparation of functionalized cyclodextrin derivatives
Mixing and grinding cyclodextrin and maleic anhydride into powder in a mortar, and carrying out esterification reaction under anhydrous condition to obtain a functionalized cyclodextrin derivative;
(2) Preparation of the copolymer
Adding a functionalized cyclodextrin derivative, azodiisobutyronitrile, vinyl acetate, styrene and tetrahydrofuran into a reaction container, condensing and refluxing under constant-temperature magnetic stirring, precipitating a copolymer by using a precipitant after the reaction is finished, filtering and drying to obtain the copolymer;
(3) Preparation of asymmetric nanoparticle-filled porous substrates
Weighing the copolymer prepared in the step (2) and dissolving the copolymer in TiCl-containing solution 4 Is prepared into casting film solution in carbon disulfide solvent, wherein TiCl 4 The mass concentration is 0.1-1%, casting film liquid is poured on a glass sheet at room temperature under the ventilation condition, and the glass sheet is kept stand to fully self-assemble, and then dried, so that the nano TiO is obtained 2 Particle-filled porous substrates;
(4) Preparation of bionic super-smooth surface filled with asymmetric nano particles
Nano TiO prepared in the step (3) is prepared 2 Immersing the particle-filled porous substrate in polydimethylsiloxane, standing the sample vertically after the silicone oil is fully injected, so that superfluous lubricating grease on the surface is lost due to the action of gravity, and obtaining the asymmetric nanoparticle-filled bionic super-smooth surface;
the molar ratio of cyclodextrin to maleic anhydride in the step (1) is 1:4-1:40.
3. The asymmetric nano TiO according to claim 2 2 The preparation method of the particle filling bionic super-smooth surface is characterized by comprising the following steps of: the reaction temperature in the step (1) is 60-85 DEG C o C, the reaction time is more than 6 h; the reaction is finished, the post-treatment step comprises washing unreacted monomers with acetone and ethanol, and suction filtration is carried out for 40-100 o And C, drying.
4. The asymmetric nano TiO according to claim 2 2 The preparation method of the particle filling bionic super-smooth surface is characterized by comprising the following steps of: in the step (2)Should deoxidize 60-80 percent o C. The adding amount of the azodiisobutyronitrile is 1% of the mass of the monomer after the reaction is carried out under the stirring condition of more than 6h.
5. The asymmetric nano TiO according to claim 2 2 The preparation method of the particle filling bionic super-smooth surface is characterized by comprising the following steps of: the precipitant in the step (2) is methanol and water in a volume ratio of 1: 1.
6. The asymmetric nano TiO according to claim 2 2 The preparation method of the particle filling bionic super-smooth surface is characterized by comprising the following steps of: in the step (3), the dropping amount of the casting solution on the glass is 50-200 mu L/cm 2 The reaction temperature is 5 to 30 o And C, the air humidity is more than 50% -80%, and the self-assembly time is more than 2 h.
7. The asymmetric nano TiO according to claim 2 2 The preparation method of the particle filling bionic super-smooth surface is characterized by comprising the following steps of: the soaking time in the step (4) is higher than 10min, and the vertical standing time is more than 24 h.
8. An asymmetric nano TiO according to claim 1 2 The application of the particle filling bionic super-smooth surface is characterized in that: as a hydrophobic material, an anti-icing material or an anti-bacterial adhesion material.
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Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1576202A (en) * | 1967-08-18 | 1969-07-25 | ||
| CN1276388A (en) * | 1999-06-04 | 2000-12-13 | 罗姆和哈斯公司 | Process for preparing intrinsic conductive copolymer and copolymer composition thereby |
| CN102248736A (en) * | 2010-05-21 | 2011-11-23 | 中国科学院化学研究所 | Method for preparing regular composite membrane and semi-spherical inorganic substance micro-nano particles |
| CN104072797A (en) * | 2014-06-27 | 2014-10-01 | 西北工业大学 | Method for preparing long-chain hyperbranched polystyrene porous membrane employing cyclodextrin functionalization |
| WO2015040426A1 (en) * | 2013-09-23 | 2015-03-26 | Tioxide Europe Limited | Titania particles and a process for their production |
| CN107174980A (en) * | 2017-06-07 | 2017-09-19 | 常州诺澜复合材料有限公司 | A kind of preparation method of cellulose lamination antibacterial ultrafiltration membrane |
| CN107446401A (en) * | 2017-04-01 | 2017-12-08 | 华南理工大学 | Using dopamine as high hydrophobicity anti-bacterial attachment surface of anchor molecule and preparation method thereof |
| CN107474199A (en) * | 2017-08-04 | 2017-12-15 | 常州大学 | A kind of preparation method of hydrophobic surface |
| CN109518162A (en) * | 2018-12-18 | 2019-03-26 | 同济大学 | A kind of preparation method of bionical net mitochondrial structure thin-film material |
| CN109627946A (en) * | 2018-12-06 | 2019-04-16 | 中国科学院海洋研究所 | A method of preparing bionical superslide surface at room temperature with self-healing properties |
| AU2020103898A4 (en) * | 2020-12-04 | 2021-02-11 | Hexi University | Method for Preparation Magnetic Porous Materials |
| JP2021063223A (en) * | 2019-10-11 | 2021-04-22 | 南京大学 | Porous cyclodextrin polymer |
| CN113480775A (en) * | 2021-07-16 | 2021-10-08 | 常州大学 | Preparation method and application of multilayer pore structure film |
| WO2022000944A1 (en) * | 2020-06-30 | 2022-01-06 | 苏州天澜生物材料科技有限公司 | Solid-liquid-filled low-surface-energy smooth functional material and preparation method therefor |
| CN114262410A (en) * | 2021-12-20 | 2022-04-01 | 常州大学 | Super-hydrophobic film based on concentration adjustment self-assembly and preparation method and application thereof |
-
2022
- 2022-04-29 CN CN202210464980.5A patent/CN114736424B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1576202A (en) * | 1967-08-18 | 1969-07-25 | ||
| CN1276388A (en) * | 1999-06-04 | 2000-12-13 | 罗姆和哈斯公司 | Process for preparing intrinsic conductive copolymer and copolymer composition thereby |
| CN102248736A (en) * | 2010-05-21 | 2011-11-23 | 中国科学院化学研究所 | Method for preparing regular composite membrane and semi-spherical inorganic substance micro-nano particles |
| WO2015040426A1 (en) * | 2013-09-23 | 2015-03-26 | Tioxide Europe Limited | Titania particles and a process for their production |
| CN104072797A (en) * | 2014-06-27 | 2014-10-01 | 西北工业大学 | Method for preparing long-chain hyperbranched polystyrene porous membrane employing cyclodextrin functionalization |
| CN107446401A (en) * | 2017-04-01 | 2017-12-08 | 华南理工大学 | Using dopamine as high hydrophobicity anti-bacterial attachment surface of anchor molecule and preparation method thereof |
| CN107174980A (en) * | 2017-06-07 | 2017-09-19 | 常州诺澜复合材料有限公司 | A kind of preparation method of cellulose lamination antibacterial ultrafiltration membrane |
| CN107474199A (en) * | 2017-08-04 | 2017-12-15 | 常州大学 | A kind of preparation method of hydrophobic surface |
| CN109627946A (en) * | 2018-12-06 | 2019-04-16 | 中国科学院海洋研究所 | A method of preparing bionical superslide surface at room temperature with self-healing properties |
| CN109518162A (en) * | 2018-12-18 | 2019-03-26 | 同济大学 | A kind of preparation method of bionical net mitochondrial structure thin-film material |
| JP2021063223A (en) * | 2019-10-11 | 2021-04-22 | 南京大学 | Porous cyclodextrin polymer |
| WO2022000944A1 (en) * | 2020-06-30 | 2022-01-06 | 苏州天澜生物材料科技有限公司 | Solid-liquid-filled low-surface-energy smooth functional material and preparation method therefor |
| AU2020103898A4 (en) * | 2020-12-04 | 2021-02-11 | Hexi University | Method for Preparation Magnetic Porous Materials |
| CN113480775A (en) * | 2021-07-16 | 2021-10-08 | 常州大学 | Preparation method and application of multilayer pore structure film |
| CN114262410A (en) * | 2021-12-20 | 2022-04-01 | 常州大学 | Super-hydrophobic film based on concentration adjustment self-assembly and preparation method and application thereof |
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